CN105939842A - Method of preparing an annular component useful as an air barrier and air barrier - Google Patents

Method of preparing an annular component useful as an air barrier and air barrier Download PDF

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Publication number
CN105939842A
CN105939842A CN201480074314.4A CN201480074314A CN105939842A CN 105939842 A CN105939842 A CN 105939842A CN 201480074314 A CN201480074314 A CN 201480074314A CN 105939842 A CN105939842 A CN 105939842A
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CN
China
Prior art keywords
edge
sheet material
ring
shaped component
seam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480074314.4A
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Chinese (zh)
Inventor
P·C·香农
M·J·芬克
P·W·曼德斯
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Publication of CN105939842A publication Critical patent/CN105939842A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
    • B29D30/44—Stretching or treating the layers before application on the drum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0019—Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/022—Mechanical pre-treatments, e.g. reshaping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/024—Thermal pre-treatments
    • B29C66/0242—Heating, or preheating, e.g. drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7318—Permeability to gases or liquids
    • B29C66/73185—Permeability to gases or liquids non-permeable
    • B29C66/73186—Permeability to gases or liquids non-permeable to gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/08—Building tyres
    • B29D30/20—Building tyres by the flat-tyre method, i.e. building on cylindrical drums
    • B29D30/30—Applying the layers; Guiding or stretching the layers during application
    • B29D30/3007—Applying the layers; Guiding or stretching the layers during application by feeding a sheet perpendicular to the drum axis and joining the ends to form an annular element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
    • B29D2030/0682—Inner liners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
    • B29D30/44—Stretching or treating the layers before application on the drum
    • B29D2030/4437—Adjusting the dimensions of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
    • B29D30/44—Stretching or treating the layers before application on the drum
    • B29D2030/4437—Adjusting the dimensions of the layers
    • B29D2030/445—Shortening the layers, e.g. by acting on the lateral edges or on the thickness or by cutting

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Method of forming an annular component useful as an air barrier comprising wrapping a sheet around a building drum to create an annular component having overlapping opposing edges thereby forming an overlapping seam, the sheet having a modulus as determined according to ASTM D412-92 greater than about 6.5 MPa, wherein the edges of the seam are modified prior to wrapping.

Description

Preparation can be used as method and the inner liner of the ring-shaped component of inner liner
Inventor: Porter C.Shannon, Michael J.Vinck, Peter W.Manders
Priority
The priority of the USSN 61/933,470 that application claims was submitted on January 30th, 2014 And rights and interests.
Technical field
The present invention relates to can be used as the ring-shaped component of inner liner.It is more particularly related to system The method being ready for use on the ring-shaped component that can be used as inner liner of tire and the application of other industrial rubber.
Background technology
The present invention relates to be used especially for tire and require what other industrial rubber impervious was applied Ring-shaped component.
Can be used as inner liner by containing material, the such as thermoplastic of dynamic vulcanization alloy (DVA) The ring-shaped component prepared is prepared as follows: extrusion-blown modling membrane tube, cuts described pipe to due size, And described pipe is inserted on assembly drum (building drum) as sleeve pipe.U.S. Patent number 5,468,444 disclose standard blown membrane technology.This kind of assembly is introduced conventional tire manufacture method In be disadvantageous, be this casing methods to be difficult to by automatization's mode and perform.
The ring-shaped component that can be used as inner liner in order to use common manufacturing method to make is suitable for tire and work Industry rubber applications, have employed sheet material method in prior art, wherein cut the blowing membrane tube of extrusion also Cut into discrete sheet material, then wrap up described sheet material round tire assembly drum so that end is heavy Folded, and by joint sealing to form seam.
Compared with casing methods, sheet material method this have the advantage that and is readily incorporated conventional tire manufacturer Method.But, sheet material method adversely contains lap seams, because film edge is before forming seam There is no taper-cut.Due to typical film thickness and the limited adhesion properties of film, conventional joint skill Art is not option.Ring-shaped component promotes and in joint adjacent area in the gross thickness of the increase of seam crossing Disadvantageous strain.It addition, the edge of seam be the most curable and therefore hinder ring-shaped component layer with Other layer in tire or industrial rubber material chemically cross-links, and this may cause joint Cracking in situ.The rigidity of this increase and non-curability can cause not satisfied tire Energy.
JP 2013-010391 discloses inner liner, and wherein the edge of at least one layer of overlapping portion is Curved, have along the circuit in tire direction and recess and protuberance.JP 2012-254718 Disclose the inner liner that a layer along overlapped surfaces contains through hole.JP 2012-254717 is open Inner liner containing the perforation through overlapping portion.There is also the example of heat-sealing lap seams.Such as, See EP2123479.
But, still demand the most also gets rid of the exposed edges of overlapping layer by the rigidity reducing overlapping portion The method overcoming the relative stiffness of ring-shaped component, arrives so that the whole length of ring-shaped component is curable On other layer in tire or industrial rubber material.
Therefore, the present invention relates to prepare and tire and the application of other industrial rubber can be used as inner liner The method of ring-shaped component to solve the strain that is associated with tire and industrial rubber manufacture and original position Cracking.
Summary of the invention
Summary of the invention
Above and/or other challenge is solved by product disclosed herein and method.
In an aspect, the method that the present invention relates to form the ring-shaped component that can be used as inner liner, Overlap is formed to produce the opposite edges with overlap including round assembly drum parcel sheet material The ring-shaped component of seam, described sheet material have according to ASTM D412-92 measure more than about The modulus of 6.5MPa, the edge of wherein said seam is modified before parcel.
In an aspect, the present invention relates to include can be used as the goods of the ring-shaped component of inner liner, Described ring-shaped component has the modulus more than about 6.5MPa measured according to ASTM D412-92, Wherein said ring-shaped component has lap seams and the described assembly thickness at described lap seam Degree is equivalent to the average thickness of described assembly.
In an aspect, the method that the present invention relates to form the ring-shaped component that can be used as inner liner, Overlap is formed to produce the opposite edges with overlap including round assembly drum parcel sheet material The ring-shaped component of seam, described sheet material have according to ASTM D412-92 measure more than about The modulus of 6.5MPa, wherein said sheet material is big from being more than or equal in the gross thickness of lap seam About 2x is reduced to about x, and wherein x is the average total thickness of described sheet material, and wherein said seam Edge parcel before modified.
Accompanying drawing is sketched
Fig. 1 depicts the blowing membrane tube with the thickness that selectivity reduces.
Fig. 2 depicts the sheet material formed by the blown film pipe of compression Fig. 1, and wherein said sheet material can As tire flap.
Fig. 3 depicts the sheet material with zigzag incision.
Fig. 4 depicts the sheet material of compacting between two cylinders.
Fig. 5 depicts by applying tension force along sheet material until it ruptures and cuts off (severed) Sheet material.
Fig. 6 a depicts the sheet material with a series of perforation.Fig. 6 b depicts by shown in Fig. 5 The sheet material of Fig. 6 a that mode is cut off.
Fig. 7 depicts the sheet material with a series of fibril (fibril).
Fig. 8 depicts by folding and roll the seam that the edge of sheet material is formed.
Fig. 9 depicts the seam formed by the edge of adjacent sheet material.
Figure 10 depicts the sheet material formed by casting films method.
Figure 11 depicts the DVA prepared by sheet material method.
Detailed Description Of The Invention
Now each specific embodiment of the present invention will be described, including in order to understand that request is protected The preferred embodiment of the present invention protected and definition.Although being specifically described this The embodiment of bright illustrative, it is to be understood that without departing from the spirit and scope of the present invention Under premise, various other improves and is apparent from and energy for those skilled in the art Enough it is easily achieved.In order to determine abuse, the scope of " present invention " refers to claims In any one or more, including their equivalent and key element or with listed those The restriction of equivalent.
The method that the present invention relates to form the ring-shaped component that can be used as inner liner, including round molding Bulge is wrapped up in sheet material and is formed the circular groups of the seam of overlap to produce the opposite edges with overlap Part, described sheet material has the modulus more than about 6.5MPa measured according to ASTM D412-92, The edge of wherein said seam is modified before parcel.
Definition
It is applicable to presently described invention and is defined as follows described.
Thickness typically refers to the thickness of single sheet.Generally, to be of about 50-big for the thickness of DVA film About 200 microns.It is said that in general, the thickness of the lap seams of liner is of about 1-about 20 millimeters. Thickness is measured according to ASTM D4805.Average thickness is measured according to ASTM D6988-13.
Gross thickness typically refers to the total amount of the thickness of each layer of the sheet material of composition ring-shaped component.Example As, the gross thickness of two sheets is 2x, and wherein x is the thickness of each layer of sheet material.
Modulus typically refers to the tendency that film or sheet material deform after applying power.M50 is used in this article Refer to 50% modulus measured according to ASTM D412-92.Higher M50 value is generally with the highest Impermeability is relevant.Generally, the M50 of DVA is of about 6.5-about 25MPa.Preferably, DVA M50 is big to being less than at about 6.8MPa or 7MPa or 7.2MPa or 11MPa or 15MPa In the range of about 18MPa or 20MPa or 25MPa.
Tubular film refers to the film can prepared by any blown film process as known in the art.Blowing The method that the limiting examples of film method includes using the cylinder of the film that can compress itself.
Sheet material or sheet material film refer to the monofilm being commonly wrapped about on roller.Sheet material film non-limiting Example including casting films, cutting along open edge and may being rolled into single film so that rolling over footpath (layflat) be the blown film of original membrane twice, along two edge slit and form two individually The blown film of diaphragm and calendered sheet.
Rigid material refers to that its rigidity is minimum rigidity cured layer rigidity when combination is in tire The material of 1.5 times.The rigidity of the per unit width of layer may be calculated modulus (such as M50) and is multiplied by The thickness of layer.The rigidity of per unit width is measured with N/m.
Polymer refers to homopolymer, copolymer, interpretation, terpolymer etc..Similarly, altogether Polymers can refer to include at least two monomer, optionally has the polymer of other monomer.Work as polymerization When thing is referred to as comprising monomer, described monomer is (the most single with the polymerized form of monomer or the derivant of monomer Body unit) polymerized form be present in polymer.But, for ease of reference, phrase comprises institute State (accordingly) monomer etc. to be used as to write a Chinese character in simplified form.
Elastomer (one or more) refers to that meeting ASTM D 1566 defines: " can be from big change Shape recover and permissible, if or be modified to it sulfuration, be substantially insoluble in (but can To swell in) material of solvent " any polymer or the compositions of polymer.Elastomer is generally also It is referred to as rubber.Term elastomer can be the most used herein with term " rubber ".Preferably If elastomer have can not by dsc measurement or it can pass through dsc measurement; be less than 40 DEG C, or preferably smaller than 20 DEG C, or the fusing point less than 0 DEG C.Preferably elastomer has and passes through DSC The Tg of-50 DEG C or lower measured.
Sulfuration or solidification refer to that the chemistry forming key or crosslinking points between the polymer chain of elastomer is anti- Should.
What dynamic vulcanization referred to make the most under high shear conditions. to exist together with thermoplastic resin can The sulfuration process of vulcanized elastomer sulfuration.Due to shear-mixed, vulcanizable elastomer cross-links also simultaneously Fine grained as " microgel " is dispersed in thermoplastic resin, and produces dynamic vulcanization alloy (“DVA”).DVA generally comprises at least one containing C4-C7The elasticity of the unit that isomonoolefin is derivative Body and at least one there is the thermoplastic resin of melt temperature of 170 DEG C-260 DEG C, wherein said bullet Gonosome is present in the continuous phase of thermoplastic resin as short grained dispersion phase.DVA's is unique special Levy and be: even if there is elastomeric component to be probably the fact that be fully cured；But still can be by often Rule rubber processing techniques extrusion, injection molding, compression molding etc. by as described in DVA process and add again Work.Waste material or flash can be collected and reprocess.
Elastomer
The elastomeric component of DVA can be selected from thermoset elastomer materials kind.For wherein expecting The impervious application of end article to be prepared, using at least one hypotonicity elastomer is the phase Hope.
Can be used for the elastomer of the mixture being derived from monomer of the present invention, described mixture is at least There is following monomer: C4-C7Isoolefin monomer and polymerisable monomer.In this type of mixture, isoolefine Hydrocarbon presses the 70-99.5wt% of total monomer in any embodiment, in any embodiment by total The 85-99.5wt% of monomer exists.Polymerisable monomer presses 30-about 0.5 in any embodiment Wt%, in any embodiment, by 15-0.5wt%, or presses 8-0.5 in any embodiment The amount of wt% exists.Elastomer is by the unit containing the monomer derived with identical weight percentage rate Amount.
Isoalkene is C4-C7Compound, their limiting examples is compound such as isobutene. (isobutylene), isobutene. (isobutene), 2-methyl-1-butene alkene, 3-methyl isophthalic acid-fourth Alkene, 2-methyl-2-butene, 1-butylene, 2-butylene, methyl vinyl ether, indenes, vinyl three Methyl-monosilane, hexene and 4-methyl-1-pentene.Polymerisable monomer can be C4-C14Polyene is such as Isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-richness Alkene, hexadiene, cyclopentadiene and pentadiene.Other polymerisable monomer such as styrene, alkyl Styrene such as p-methylstyrene and dichlorostyrene are also suitable for preparing useful elastomer.
The preferred elastomer that can be used for present invention practice includes elastomer based on isobutene..Based on The elastomer of isobutene. or polymer refer to the repetition comprising at least 70mol% derived from isobutene. The elastomer of unit and at least one other polymerizable unit or polymer.Described based on isobutene. Copolymer can be by halogenation or can not be by halogenation.
In any embodiment of the present invention, elastomer can be butyl-type rubber or branched butyl The halogenation pattern of type rubber, particularly these elastomers.Useful elastomer is unsaturated butyl rubber Glue such as alkene or isoalkene and the copolymer of polyene.Can be used for the method and composition of the present invention The limiting examples of unsaturated elastic body be poly-(isobutylene-co-isoprene), poly-isoamyl Diene, polybutadiene, polyisobutylene, poly-(styrene co-butadiene), natural rubber, star Shape branched butyl and their mixture.Useful elastomer in the present invention can be by this In field prepared by known any applicable means, and the present invention is not herein limited by and prepares elastomer Method limits.Butyl rubber is by making isobutene. and 0.5-8wt% isoprene, or makes isobutene. Remaining the weight percent source obtaining polymer is reacted with 0.5wt%-5.0wt% isoprene From in isobutene.；Described butyl rubber contains the unit of the monomer derived with identical weight percentage rate Amount.
The elastic composition of the present invention can also comprise at least one containing C4-C7Isoalkene and alkyl The random copolymer of styrene co-monomer.Described isoalkene can be selected from any listed above C4-C7Isoolefin monomer, and preferably isomonoolefin, and can be different in any embodiment Butylene.Ring-alkylated styrenes can be containing at least 80wt%, more or at least 90wt% para-position isomery The p-methylstyrene of body.Random copolymer can optionally include functionalized interpolymer.Sense Change interpretation and there is at least one or more alkyl substituent being present in styrenic monomer units； Described substituent group can be benzylic halogen or some other functional groups.In any embodiment, poly- Compound can be C4-C7Alpha-olefin and the random elastomeric copolymer of alkylstyrene comonomer. Alkylstyrene comonomer can be containing at least 80wt%, more or at least 90wt% para-position is different The p-methylstyrene of structure body.Random copolymerization monomer can optionally include functionalized interpolymer, At least one or more being wherein present in the alkyl substituent in styrenic monomer units contains Halogen or some other functional groups；The styrene of the para-orientation being present in atactic polymer structure At most 60mol% can functionalised.Or, in any embodiment, the para-position existed Substituted cinnamic 0.1-5mol% or 0.2-3mol% can functionalised.
Functional group can be that halogen maybe can pass through other group such as carboxylic acid；Carboxylic salts；Carboxyl ester, acyl Amine and acid imide；Hydroxyl；Alcohol root；Phenol root；Mercaptan root；Thioether；Xanthan acid group；Cyanogen root；Cyanogen Acid group；Amino and their mixture the nucleophilic displacement of fluorine of any benzylic halogen is introduced some its Its functional group.In any embodiment, elastomer comprises isobutene. and 0.5-20mol% to first The cinnamic atactic polymer of base, at most the 60 of the methyl substituents being wherein present in benzyl rings Mol% halogen (such as bromine or chlorine), acid or ester functional.
In any embodiment, when the mixing at reactive temperature of DVA component, on elastomer Functional group make it can be with functional group present in thermoplastic resin via selecting, such as, acid, Amino or hydroxy functional group react or form polar bond.
Other hypotonicity elastomer being suitable for is the elastomer containing isobutene., such as isobutene .-different Pentadiene-ring-alkylated styrenes terpolymer or the isobutylene-isoprene-ring-alkylated styrenes of halogenation Terpolymer, wherein for each of in these terpolymers, different in terpolymer The component that butylene derives is the 70-99wt% monomeric unit in described polymer, and isoprene derives Component be the 29-0.5wt% monomeric unit in described polymer, the group that ring-alkylated styrenes is derivative Dividing is the 29-0.5wt% monomeric unit in described polymer.
The C being suitable for4-C7The derivative elastomer of isoalkene (includes the isobutene. of bromination-to methylbenzene second Alkene copolymer) have at least about 25,000, preferably at least about 50,000, preferably at least about 75,000, preferably at least about 100,000, preferably at least about 150, the number-average molecular weight of 000 Mn.Described polymer can also have less than about 6, preferably less than about 4, more preferably less than The weight average molecular weight (Mw) of about 2.5, most preferably less than about 2.0 and number-average molecular weight (Mn) Ratio, i.e. Mw/Mn.In another embodiment, the halogenated isobutylene elastomer group being suitable for Divide and include having 30 or bigger, or 125 DEG C of Mooney viscosities (1+4) of more preferably 40 or bigger are (logical Cross ASTM D 1646-99 measure) copolymer (isobutene .-p-methylstyrene of such as bromination is common Polymers).
Preferably elastomer includes isobutene. and the copolymer to ring-alkylated styrenes, and they can be with halogenation Maybe can there is no halogenation.Preferably, isobutene. and the copolymer to ring-alkylated styrenes are halogenations. This type of elastomer is described in European Patent Application No. 0344021.Described copolymer preferably has base Distribution is formed uniformly in basis.The preferred alkyl of ring-alkylated styrenes structure division is included containing 1-5 The alkyl of individual carbon atom, the primary haloalkyl containing 1-5 carbon atom, secondary haloalkyl and they Mixture.Preferably copolymer comprises isobutene. and p-methylstyrene.Isobutene. and to methylbenzene The preferred brominated copolymer of ethylene includes having 5-12wt% p-methylstyrene, 0.3-1.8 125 DEG C of Mooney viscosities of mol% brominated p-methylstyrene and 30-65 (1+4) are (by ASTM D 1646-99 measure) those.
Thermoplastic resin
For the object of the invention, thermoplastic (or referred to as thermoplastic resin) is to have at 23 DEG C The thermoplastic polymer of the Young's modulus more than 200MPa, copolymer or their mixture.Institute State resin and should have about 160 DEG C-about 260 DEG C, preferably smaller than 260 DEG C, more preferably less than The melt temperature of about 240 DEG C.In a preferred embodiment, thermoplastic resin should have There is the molecular weight of 13,000-50,000.According to usual definition, thermoplastic is upon application of heat Soften and recover after the cooling period the synthetic resin of its original performance.
This type of thermoplastic resin can be used alone or be applied in combination and usually contain can be with aromatics Nitrogen, oxygen, halogen, sulfur or the halogen of other group, such as acidic-group that functional group interacts. Be suitable for thermoplastic resin include selected from polyamide, polyimides, Merlon, polyester, polysulfones, Polylactone, polyacetals, acrylonitrile butadiene styrene resin (ABS), polyphenylene oxide (PPO), poly- Diphenyl sulfide (PPS), polystyrene, styreneo-acrylonitrile resin (SAN), phenylethylene-maleic anhydride Resin (SMA), aromatic polyketone (PEEK, PED and PEKK), ethylene copolymer resin (EVA or EVOH) Resin with their mixture.
The polyamide (nylon) being suitable for comprises crystallization or resinous, high molecular solid polymer, There is in being included in polymer chain the homopolymer of repetition amide units, copolymer and terpolymer. Polyamide can be prepared as follows: by one or more ε lactams such as caprolactam, ketopyrrolidine (pyrrolidione), lauryl lactam and aminoundecanoic lactam, or aminoacid polymerization, Or binary acid and diamidogen are condensed.The nylon of fibroblast and molding grade is all applicable.Polyamide Example includes polycaprolactam (nylon-6), polylauryllactam (PA-12), poly-six methylenes Base adipamide (nylon-6,6), polyhexamethylene nonanedioyl amine (nylon-6,9), poly-six methylenes Base decanediamide (nylon-6,10), polyhexamethylene 12 carbon diamides (nylon-6,12), poly-six Isophthalamide (nylon-6, IP) and the condensation product (Buddhist nun of 11-amino-undecanoic. acid Dragon-11).Commercially available polyamide may be advantageously used with present invention practice, wherein softening point or molten Point linear crystalline polyamides between 160-260 DEG C is preferred.
The polyester being suitable for that can use includes in the aliphatic series of anhydride or aromatic polycarboxylic acid ester one Kind or mixture and glycol in a kind of or polymeric reaction products of mixture.Gratifying poly- The example of ester includes poly-(anti-form-1,4-cyclohexylidene C2-6Alkane dicarboxylic ester the most poly-(anti-form-1,4- Cyclohexylene succinate) and poly-(anti-form-1,4-cyclohexylidene adipate ester)；Poly-(cis or anti- Formula-1,4-cyclohexanedimethyleterephthalate) the most poly-(cis-1,4-hexamethylene-two methylene of alkane dicarboxylic ester Base) oxalate and poly-(cis-1,4-hexamethylene-dimethylene) succinate, poly-(C2-4Alkylidene Terephthalate) such as polyethylene terephthalate and polytetramethylene-terephthalate, Poly-(C2-4Alkylidene isophthalate) such as polyethylene glycol isophthalate and polytetramethylene-isophthalic Dicarboxylic acid esters and similar material.Preferably polyester is derived from aromatic dicarboxylic acid such as naphthalenedicarboxylic acid or neighbour Phthalic acid and C2-C4Glycol, such as polyethylene terephthalate and poly terephthalic acid fourth Diol ester.Preferably polyester will have the fusing point of 160 DEG C-260 DEG C.
Poly-(phenylene ether) (PPE) resin that can be used according to the invention is known, it Be the commercially available material prepared by the oxidative coupling polymerization of the substituted phenol of alkyl.They are usual Be glass transition temperature be straight chain, the amorphous polymer of 190 DEG C-235 DEG C.
The ethylene copolymer resin that can be used for the present invention includes the beta-unsaturated esters of ethylene and low-grade carboxylic acid And the copolymer of carboxylic acid itself.Especially, ethylene and vinyl acetate or acrylic acid can be used The copolymer of Arrcostab, such as acrylic acid methyl ester. and ethyl acrylate.These ethylene copolymers are usual Comprise about 60-about 99wt% ethylene, preferably approximately 70-95wt% ethylene, the most greatly About 75-about 90wt% ethylene.Statement used herein " ethylene copolymer resin " is typically Refer to ethylene and rudimentary (C1-C4) monocarboxylic beta-unsaturated esters and described acid itself；Such as acrylic acid, Vinyl esters or the copolymer of alkyl acrylate.It also means that include " EVA " and " EVOH ", They refer to vinyl-vinyl acetate copolymer, and their hydrolysis homologue ethylene-vinyl alcohol.
In dynamic vulcanization alloy, thermoplastic resin presses about 10-98wt%, implements at another In scheme, the amount of about 20-95wt% exists, based on alloy blend.Another embodiment party In case, thermoplastic resin is pressed the amount of 35-90wt% and is existed.Elastomer amount in DVA is by about 2-90wt%, in another embodiment, the amount of about 5-80wt%, it is blended based on alloy Thing.In any embodiment of the present invention, elastomer is pressed the amount of 10-65wt% and is existed.At this In invention, thermoplastic resin is present in alloy by the amount of 40-80phr, relative to elastomer Amount.
Auxiliary elastomer
In some embodiments, DVA can comprise auxiliary elastomer further.Auxiliary elastomer is permissible It is any elastomer, but preferred auxiliary elastomer is not the elastomer containing isobutene..Preferred auxiliary bullet The example of gonosome is maleic anhydride modified copolymer.Preferably, auxiliary elastomer is containing maleic anhydride With the copolymer of ester functional group, the most maleic anhydride modified ethylene-ethylacrylate.
Can be by auxiliary elastomer simultaneously together with initial elasticity body and thermoplastic resin initial feed stream Add in DVA processing extruder.Or, can add it at described elastomer with initial Thermoplastic resin raw materials flows down in the extruder of trip.
Auxiliary elastomer amount in DVA can be in the range of about 2wt%-about 45wt%. If DVA comprises at least one elastomer and auxiliary elastomer, then elastomer and auxiliary elastomer Total amount is preferably in the range of about 2wt%-about 90wt%.
This auxiliary elastomer can solidify together with main elastomer based on isoalkene or it is permissible Via selecting holding uncured and serving as the bulking agent being discussed below.
Other DVA component
Other material can be blended in DVA the preparation to help DVA or provide for described DVA Desired physical property.These additional materials include, but not limited to firming agent, stabilizer, Bulking agent, reactive plasticizer, non-reacted plasticizer, extender and polyamide oligomer as well as or low Molecular weight polyamide, such as United States Patent (USP) 8, described in 021,730B2.
The solidification of main elastomer is generally reached by introducing firming agent and non-essential accelerator, Qi Zhongren The master mix of what this type of component is referred to as curing system or solidification package.The curing component bag being suitable for Include sulfur, metal-oxide, organo-metallic compound, radical initiator.Conventional firming agent includes ZnO、CaO、MgO、Al2O3、CrO3、FeO、Fe2O3And NiO.These metal-oxides can be single Solely use or with metal stearate salt complex (such as, the stearate of Zn, Ca, Mg and Al) In conjunction with, or with stearic acid or other organic acid and sulfur-containing compound or alkyl or aryl per-compound or Diazonium radical initiator is used in combination.If use peroxide, can use commonly used in the art Peroxide auxiliary agent.If thermoplastic resin is so that there is peroxide will make described thermoplastic resin The thermoplastic resin of fat crosslinking, then can avoid using peroxide firming agent.
As noted, accelerator (also known as accelerator) can be added with shape together with firming agent Become solidification package.Be suitable for firming agent accelerator include amine, guanidine, thiourea, thiazole, thiuram, Sulfenamide, sulfenimide, thiocarbamate, xanthate etc..Many accelerator are As known in the art and include, but are not limited to following material: stearic acid, diphenylguanidine (DPG), Tetramethylthiuram disulfide (TMTD), 4,4'-dithio morpholine (DTDM), curing four fourth Base thiuram (TBTD), 2,2'-benzothiazole disulfide (MBTS), hexa-methylene-1,6-double sulfur generation Sulfuric acid disodium salt dihydrate, 2-(morpholinothio) benzothiazole (MBS or MOR), 90%MOR Compositions, the N-tert-butyl group-2-[4-morpholinodithio sulfenamide with 10%MBTS (MOR 90) (TBBS), N-(1,3-dimethylbutyl)-N '-phenyl-p-phenylenediamine (6PPD) and N-oxygen two Ethylidene thiocarbamoyl-N-oxygen diethylidene sulfonamide (OTOS), 2 ethyl hexanoic acid zinc (ZEH), N, N'-diethyl thiourea.
In any embodiment of the present invention, at least one firming agent is generally by about 0.1-about 15phr；Or about 1.0-about 10phr, or about 1.0-6.0phr, or about 1.0-4.0 Phr, or about 1.0-3.0phr, or about 1.0-2.5phr, or about 2.0-5.0phr Exist.If only using single curing agent, then it is preferably metal-oxide such as zinc oxide.
Can add and include low with the component by the viscosity increase-volume between elastomer and thermoplastic component Molecular weight polyamide, there is the maleic anhydride glycerol polymerization of the molecular weight of about 10,000 or bigger Thing, methacrylate copolymer, tertiary amine and secondary diamine.One group of conventional bulking agent includes Malaysia Acid anhydride-grafted ethylene-ethyl acrylate copolymer (can be from Mitsui-DuPont as having root The solid obtained according to the AR-201 of the melt flow rate (MFR) of the 7g/10min of JIS K6710 measurement Rubber-like material) and butyl benzyl sulfonamide and polyisobutylene succinic anhydride.These compounds can To be used for increasing thermoplastic " effectively " amount in elasticity/thermoplasticity blend.Select additive Amount with obtain desired viscosity contrast, without negatively affect DVA characteristic.If there is too Many additives, then impermeability may reduce and may must remove adding of excess during post-treatment Add agent.If there is inadequate bulking agent, then elastomer may will not phase inversion to become thermoplasticity Dispersion phase in resin matrix.
Reactive and non-reacted plasticizer can serve as bulking agent due to the character of plasticizer.Heat The plasticizer of thermoplastic plastic is normally defined and adds in polymeric material to improve flexible, extensibility Compound with machinability.Known and conventional thermoplasticity plasticizer is in as little as high viscosity liquid The supply of form also can be with functionalization.Many different plasticizers are known as in thermoplastic resin field From each analog thermoplastic resin, there is the different compatibility and the performance to thermoplastic resin has different The plasticizer of impact.Known thermoplasticity plasticizer includes different types of ester, hydrocarbon (aliphatic series, ring Alkane and aromatics), polyester and condensation polymer；See thermoplastic elastomer (TPE) handbook (Handbook of Thermoplastic Elastomers),Jiri George Drobny,p.23(William Andrew Publishing,2007).For polyamide, it is known that non-reacted plasticizer include By tertiary amine, secondary diamine or the hydrocarbon of sulfonamide functionalization.
The method preparing DVA
For having the thin film being ready to use in the type preparing tire flap, the form of DVA is in the phase of acquisition Hope that aspect of performance is important.The form of DVA depends on mixing condition, including temperature, imports into Order, the time of staying and the shear rate divided.
Double screw extruder is preferred melt process equipment.Extruder preferably has along extruder Length arrange at least two engagement and homodromal screw rod.It is at least in one end of extruder The feed throat that a kind of raw material stream (main thermoplastic resin raw materials stream and/or elastomer material stream) flows into. Resin in this raw material stream or elastomer can be prepared as before entering extruder or can not It is prepared as masterbatch.Along the length of extruder, other component is fed system.
It is standby that DVA can have more than the extrusion mechanism of two screw rods with apparatus, and can also have U.S. Put into practice on the ring screw extruder of type disclosed in state's patent 7,655,728.
After having mixed DVA formation alloy, DVA leaves extruder and through for being sent by DVA The smelt gear pump prepared through downstream process.
DVA has the stiffness/unit width more than about 340N/m.Preferably, DVA has greatly Stiffness/unit width in about 580N/m.Preferably, DVA has more than about 1360N/m Stiffness/unit width.It is further preferred that DVA has the stiffness/unit width more than about 2320N/m Degree.
DVA has the Xiao Er A hardness more than 70 measured according to ASTM D2240.Preferably, DVA has the Xiao Er A hardness more than 75 measured according to ASTM D2240.Preferably, DVA There is the Xiao Er A hardness more than 80 measured according to ASTM D2240.It is further preferred that DVA has The Xiao Er A hardness more than 85 measured according to ASTM D2240.
Although relating to DVA, but those of ordinary skill in the art will be appreciated by other high stiffness material, It is public that such as thermoplastic elastomer (TPE), TPV and thermoplastic film can also be advantageously used in institute The joint technique of the present invention opened.The limiting examples of other material that can use includes Disclosed in EP2610072, WO2013/093608, United States Patent (USP) 8,188,187 and EP2574635 Those.
Preparation has the ring-shaped component of uniform gross thickness at lap seam
Can be used as in tire and industrial rubber application as it was earlier mentioned, sheet material method is generally used for assembling The ring-shaped component of inner liner.In this kind of method, the blowing membrane tube of extrusion is cut and cut into Discrete sheet material, then makes described sheet material wrap up round tire assembly drum, has overlapped ends, and Joint sealing is formed seam.For the purpose of the application, the method for this insertion DVA blown film Should be so-called " conventional method ".The shortcoming using above-mentioned sheet material method is that ring-shaped component is connecing The thickness increased at seam will cause and disadvantageous strain in joint adjacent area.
Figure 11 depicts the DVA prepared by said method, obtains having the interior of lap seams 100 Lining 110.During the formation of tire and the bending rotating tire of solidification, liner strains. In overlapping region 100, strain in two overlapping layers disperse, but strain in fact concentrated on , there is the less material absorbing strain there in point 102.Away from the position of strain location 102, Such as putting 104, the strain of material reduces.When liner is formed and when owing to repeating by rigid material When the strain bent and stand is more than the recovery capability of material, material experience permanent deformation, thus produce The region of raw potential failure.It addition, overlapped ends A of DVA liner and B are not curable rubbers Glue and therefore hinder ring-shaped component layer chemically with tire (maybe when in other goods, Industrial rubber) in other layer crosslinking, consequently, it is possible to cause the original position in joint to ftracture.
Fig. 1 depicts blowing membrane tube 10, and wherein the film 10 thickness in position 12 reduces, described Position 12 will form the lap seams of liner.Can by use contain as is generally known in the art one or The blow moulding equipment of multiple breach reduces the film thickness at these positions 12.Blow when using described equipment When moulding the pipe with average thickness 0.5x, one or more breach in the blown film of gained at breach The thickness y reduced is produced at region.It is average thickness that the thickness y of the reduction formed in blown film has The value of the 0.4-0.6 of degree 0.5x.
In one embodiment, blown film can be heated into melt, then pressurization is to subtract The gross thickness of little lap seams.After obtaining blowing membrane tube as shown in Figure 1, described pipe 10 can Monolayer is formed to flatten.Can flatten symmetrical for film 10 so that the central point of non-seam section is the most straight Earth Phase pair.The width so having the effect that each doubling seam section is the one of original width Half, because folding footpath is folded across the center of described seam section.
In one embodiment, film 10 can the most asymmetric flattening.Fig. 2 retouches Paint the sheet material 20 that the blown film pipe by compressing Fig. 1 at the broken line A-A ' place of Fig. 1 is formed, its Described in sheet material can be used as tire flap.Compress blown film by online A-A ' place, then use Sheet material method prepares above-mentioned ring-shaped component, and the edge 22 and 24 of sheet material 20 has the total thickness of reduction Degree y.The lap seams formed by edge 22 and 24 will have a uniform gross thickness, described uniformly Gross thickness is consistent with gross thickness x of other section of ring-shaped component.
In two embodiments symmetrically or non-symmetrically flattened, the seam section of folding will roll over footpath at film Edge on.In the case of monofilm, then described film can be heated to more than its fusing point warp Sealed by any method producing pressure as is generally known in the art.In the case of multilayer film, because interior The fusing point that layer has less than any layer of described film does not serve as air barrier, so innermost layer will Melt and seal, and remainder layer will keep non-melt.Therefore, for multilayer film, it is possible to use ring Should be in stimulating the such as innermost layer of chemical reaction with itself for the UV of solidification.
The edge of assembly was modified before forming seam
As it has been described above, the sheet material method of routine has the gross thickness of increase at seam crossing, this cause with Disadvantageous strain in the region that joint is adjacent.Adjunctively or alternatively said method, via sheet material method After blowing membrane tube 10 is cut into discrete sheet material 20, edge 22 He of described sheet material can be modified 24 high stress concentrations that not so can occur with reduction, described high stress concentrations is in edge 22 and 24 shape Will exist when becoming lap seams.The various non-limiting method that may be used for modifying module edge exists This is open.
Fig. 3 depicts the sheet material 20 at edge 22a with zigzag incision.An embodiment party In case, zigzag incision can be produced along sheet edge 22a as follows: at two, there is interlocking Described material is sheared between the blade of V-arrangement profile.If this type of blade is a part for Manual knife, The most described blade rotates round the axle being perpendicular to cut direction, and the shape of the tooth on described blade Shape must be allowed for these actions.But, in order to cut DVA film with automation mechanized operation, will preferably adopt With the blade of at least incision length, and it is being perpendicular to film as in cutting machine or electric power shears Mobile one or both of which on the linear track of plane.Or, it is possible to use there is sawtooth The rotary knife cutter of shape.The average stiffness of sheet edge 22a is the function of the position of cutting sheet material, The wherein average stiffness of sheet edge 22a otch to be compared at the bottom position of zigzag incision 26 The top of 28 is big.
Fig. 4 depicts the sheet material 20 of compacting between two cylinders 30 and 32.Although Fig. 4 describes Cylinder, but any equipment as known in the art may be used for suppressing sheet material 20, such as two Plate or a cylinder and a plate.In one embodiment, DVA sheet material 20 can be produced as follows Thinning edge 22b: two the heating cylinders 30 and 32 alignd with cut direction at its axis Between suppress sheet material 20, to cause described sheet edge 22b melted and along with the gap between cylinder Close and extrude, thus form thinning edge 22b.Or, it is also possible to sheet material 20 is when it relatively Suppress single cylinder when supporting onboard or there is the plate of intimate dot profile, and not gluing release coating Or film can be used for preventing melted sheet edge 22b from pasting on one or two instrument.Business is moulded The antiadhesion barrier being suitable for used in material film phonograph seal machine is the weaving glass fibers being impregnated with politef Dimensional fabric.
Fig. 5 depicts by applying, along assembly, the sheet material 40 that tension force cuts off until its fracture.Subtract Thin and cutting can be crossed sheet material 40 and be carried out simultaneously, it is preferable that method uses one or more The roller (a traversing profiled roller) 34 crossing profile replaces display in Fig. 4 One or two in cylinder or plate.During this kind performs, roller 34 will move across sheet Material, produces cutting, and wherein roller axis 36 is parallel with the sheet material of sheet material 40 and lead.This Sample is perpendicular to, by thiing have the advantage that requirement is more waited a little while,please, the power that sheet material 40 applies, but cutting will flower Take longer time generation.In the case of the roller of heating, bearing must be transported at elevated temperatures Turn or provide some devices to keep bearing cooling.
And the pressure between its dependence instrument produces the thinning of sheet material 40 and is finally recovered, not as executing Add tension force in be heated to close to or any surface of slightly higher than narrow section of its fusing point, and cause it Constriction the thinning edge left.Can heat described narrow bar thing as follows: by with The heat conduction of hot surface contact, suitably processes or protects against stickup；Such as passed through by convection current From otch or the impact of the steam of series of apertures；By radiation such as close to surface thermal radiation or pass through Oriented energy bundle such as laser；Or heated by the electrolyte in the herring bone of alternating electric field.These The heating of form can be crossed sheet material 40 simultaneously and be applied, or applies partly, allows sheet material 40 with gradually Enter or tear motion mode to separate.
Overlapping edge 22 is made to become a series of conical point with 24 and/or make the thickness of sheet material at edge Locate tapered the embodiment above can be combined in such a operation, described operation melting at film The sheet edge 22 of Fig. 2 is become the taper of a series of extension by point below and above with 24 downward drawing-offs Point.When DVA sheet material is the blowing membrane tube by compression or the continuous sheet 20 of casting films sheet material formation During with 40, these methods are useful.Above-mentioned taper method can be carried out as follows: to be perpendicular to cut Cut a series of holes 42 or chopped mouth 44 or the combinations thereof stamping-out sheet material 40 of direction orientation, such as figure Shown in 6a.When any surface of the line along perforation 42 or 44 applies tension force, the film between perforation Lead-in wire extend and be necked to breakdown point, as shown in Figure 6 b.Then by mode as shown in Figure 5 Cut off sheet material 40.Various devices may be used for producing the line of perforation 42 and 44, such as, be arranged in pen Nozzle needle in straight carrier or cutterhead and blade, laser ablation etc..Otch 42 or cave can be used to wear One or more lines in hole 44 are to produce the shape desired by downward drawing-off one-tenth and reducing final wheel The lead-in wire of the stress in tire liner.In the case of fluid cuts, it is possible to use shell manifests pressure, Or can towards sheet material 40 with projected at high velocity fluid so that fluid dynamic be enough to perforation 42 and 44 at make Sheet fractures.If solid particle is entrained in fluid streams, as common in water-jet cutting technology Like that, then the effect of this type of fluid can be strengthened.
Except producing in addition to defiber, additional interval can be provided at random or patterned location Bore a hole to produce the device during curing discharged from the goods formed by the air of trapping.Due to The during curing flowing of DVA, this type of perforation can during curing selfreparing.
With it as the stress reduction feature of the integrated result generation sheet edge of cutting sheet material, it is not so good as First pass through conventional method cutting sheet material and add stress reduction feature as independent operation.? The edge of cutting can be by thinning tapered facing to grinding belt or drum mechanical grinding.Above-mentioned various dress Put the cut edge that can also be applied to sheet material, be included between instrument, or cross sheet material simultaneously, Or little by little heat via the conversion of partial operation and be pressed into taper, by gas or liquid jet Such as water spray possibly tapered or fibrillation.Line brush wheel may be used for abrasion, fibrillation and stretching thinning Edge, it is supported on stiffer wear-resistant surface simultaneously.Make band or yarn abrasion and the method for fibrillation It is described in INEOS Olefins&Polymers Polypropylene Processing Guide, p In 9.Fig. 7 depicts the sheet material 50 being prepared with a series of fibril 52.
Improve the bonding of ring-shaped component and other layer in tire
As it was earlier mentioned, the edge that another shortcoming that conventional sheet method runs into is seam can not be consolidated Change, and therefore hinder ring-shaped component layer to hand over other stratification in tire or industrial rubber material Connection, this may cause the original position in joint to ftracture.
If the blown film of Fig. 1 is the two membranes with curable rubber outer layer, then in such as Fig. 2 When it is compressed to form sheet material like that, the whole outer surface of Fig. 2 is also curable.If will figure The blown film of 1 is extruded together with adhesive exterior and rubber curable layer, then exist when adhesive exterior Time between DVA sheet material and described rubber curable layer, the compression sheet material in Fig. 2 will have six layers, Including sheet material described in outer rubber curable layer, adhesive phase, two-layer, additional adhesive phase and attached The outer rubber curable layer added.
At least one binding agent body based on epoxidation vinyl benzene butadiene styrene block copolymerization thing System uses sulfur curable agent to be diffused in adhesive phase from adjacent rubber layer, in order to carry out DVA sheet Material and the crosslinking of rubber layer, this is important for long durability and the high-temperature behavior of tire product 's.Because DVA sheet material is the obstruct to this diffusion needed for adhesive composition, so In the lap seams 100 of Figure 11, the binding agent of trapping will have the lowest performance.One In individual embodiment, above-mentioned various methods can be used in the region of the lap seams 100 of Figure 11 The new surface area that removing original adhesive layer and/or generation add (such as by downward drawing-off film, makes Its fibrillation or rupture) so that whole DVA sheet material can be with other in tire or industrial rubber material Layer solidifies together.
In one embodiment, the adhesive exterior making sheet material bond it is used for adjacent rubber layer Can be combined glue (ATG) (adhesive tie-gum) to constitute by binding agent, described binding agent combines Glue contains especially for promoting becoming of the adhesion of the sheet material coated with resorcinol formaldehyde latex (RFL) Point.The example of RFL adhesive coating and ATG preparation provides in the prior art.But, when with During RFL binding agent coating ring-shaped component, these adhesion promoting compositions increase cost also can not be in institute Lower requirement that there is something special.In one embodiment, the fillet of ATG can be applied in engaging zones Shape thing, and the remainder of the blend contacted with the liner of RFL coating will be lower cost preparation. Or, the composition making ATG and standard carcass blend distinguish (includes phenol formaldehyde resin, isophthalic Diphenol, resorcinol formaldehyde resin, formalin and hexamethoxy methyl cyanuramide) can put on and connect Closing on the DVA in region, the standard carcass being diffused into surrounding from described engaging zones is compounded by they In thing, and it is effectively converted into ATG preparation.
In one embodiment, by many blown film (at the overlap 100 of Figure 11 tapered after) Dip-coating is in the material being cured to both DVA film layer and rubber.Such as, if described functional material Material is DVA based on nylon, and the most described dipping layer can be appointing described in WO 2012/134454 What example.
In one embodiment, the blown film described in casting films rather than Fig. 1 is used to prepare DVA film.Figure 10 depicts casting films method, and wherein dark limb 54 and 56 represents encapsulating die head, Such as derive from those of Cloeren Technology.Using casting films as known in the art After equipment prepares film, transversely (represented by dotted line 58) and cut it, so that the edge of extruded film is Rubber is curable.When forming endless shaper article such as flexible pipe or tire flap, can be by the past Any method described reduces the thickness of film edge to reduce the overlapping gross thickness of gained.
The method forming seam
In some prior aries, seam edge A and the B without adhesive coating are embedded in adjacent Material other layer in, including sheet material itself.Fig. 8 depicts wherein by folding and rolling sheet This kind of embodiment of the seam that the edge of material is formed.It is said that in general, when parcel is so that in tire Total stress is concentrated when minimizing, and it is favourable for making the sum of the layer in lap seams 106 minimize. But, in the present embodiment, compacting seam permits to the thickness similar to ring-shaped component itself subsequently Permitted the multilamellar in seam to use.This kind of thickness reduce can by with above the edge making sheet material is become Similar technique and equipment that taper describes reach.Can heat and suppress described double-fold seam to subtract Its thickness little, then cools down.The edge being to increase film is perpendicular to pressing direction by the result of this kind of compacting The size in direction, this small increase that will cause crossing over sheet material (along seam direction), but will lead Cause to be perpendicular to more the dramatically increasing along the circumferential direction of the length of seam, i.e. tire assembly drum.This can Can be undesirable, because when wrapping up round assembly drum, it will make sheet material loose, thus lead Cause when the succeeding layer of tire being wound on it above wrinkling.Or, sheet material can be placed in institute State the amount below its pre-stretch-draw when rousing upper: described amount be enough to absorb by compacting seam 106 downwards Produce is lax.This kind of pre-stretch-draw of sheet material can have the additional advantage that what interim generation added Lax so that the folding of double-fold seam, and by from assembly drum internal suction, or can pass through In position facing to sheet material described in described bulging mechanical grip.In one embodiment, seam can With by making the edge of sheet material abut to form as shown in Figure 9.By either method described herein Formed before seam, the edge of assembly can as before disclosed in process.
Particular
The present invention can also understand according to following specific embodiment:
Section A: the method forming the ring-shaped component that can be used as inner liner, including round molding bulge Wrap up in sheet material and form the ring-shaped component of the seam of overlap, institute to produce the opposite edges with overlap State sheet material and there is the modulus more than about 6.5MPa measured according to ASTM D412-92, wherein The edge of described seam is modified before parcel.
The method of section B: section A, wherein said sheet material is blown film or casting films.
The method of section C: section A, wherein said edge by producing a series of saws along described edge Teeth cutouts is modified.
The method of section D: section A, wherein said edge is modified by suppressing described edge.
The method of section E: section D, wherein said edge is heated before pressing.
The method of section F: section A, the wherein described edge of following modification: along the length of described sheet material Apply tension force until its fracture is by described sheet cutting.
The method of section G: section F, produces a series of perforation the most before cutting along described edge.
The method of section H: section A, wherein said edge by producing a series of fibres along described edge Silk is modified.
The method of section I: section A, wherein said ring-shaped component is dynamic vulcanization alloy.
Section J: including the goods that can be used as the ring-shaped component of inner liner, described ring-shaped component has root The modulus more than about 6.5MPa measured according to ASTM D412-92, wherein said ring-shaped component There is lap seams and described assembly and be equivalent to described assembly at the thickness of described lap seam Average thickness.
Section K: the method forming the ring-shaped component that can be used as inner liner, including round molding bulge Wrap up in sheet material and form the ring-shaped component of the seam of overlap, institute to produce the opposite edges with overlap State sheet material and there is the modulus more than about 6.5MPa measured according to ASTM D412-92, wherein Described sheet material is reduced to about x in the gross thickness of lap seam from more than or equal to about 2x, its Middle x is the average total thickness of described sheet material, and the edge of wherein said seam parcel before through repairing Decorations.
The method of section L: section K, wherein said edge by producing a series of saws along described edge Teeth cutouts is modified.
The method of section M: section K, wherein said edge is modified by suppressing described edge.
The method of section N: section M, wherein said edge is heated before pressing.
The method of section O: section K, the wherein described edge of following modification: along the length of described sheet material Apply tension force until its fracture is by described sheet cutting.
The method of section P: section O, produces a series of perforation the most before cutting along described edge.
The method of section Q: section K, wherein said edge by producing a series of fibres along described edge Silk is modified.
The method of section R: claim K, wherein said ring-shaped component is dynamic vulcanization alloy.
Section S: the goods formed by the method for section K.
The method of section T: section K, is additionally included in described assembly and adhesive exterior in blow moulding equipment Extruding together with rubber curable layer, wherein said adhesive phase can at described assembly and described rubber Between cured layer, to form tubular products；With compression (collapsing) described tubular products with shape Becoming sheet material, wherein said sheet material contains at least six layer, including outer rubber curable layer, binding agent Assembly, extra adhesive phase and extra outer rubber curable layer described in layer, two-layer.
The method of section U: section T, wherein said adhesive exterior is constituted by selected from following material: Binding agent combines glue, resorcinol formaldehyde latex, phenol formaldehyde resin, resorcinol, isophthalic two Fluosite, formalin and hexamethoxy methyl cyanuramide.
The method of section V: section K, is additionally included in described assembly and binding agent one in casting films equipment Play extrusion.
The method of section W: section V, wherein said binding agent is constituted by selected from following material: bonding Agent combines glue, resorcinol formaldehyde latex, phenol formaldehyde resin, resorcinol, resorcinol first Urea formaldehyde, formalin and hexamethoxy methyl cyanuramide.
Herein cited all priority documents, patent, publications and patent applications, test procedure It is consistent with the present invention and this for allowing that (such as ASTM method) and other file are disclosed thing It is fully incorporated by reference in the degree of all permissions introduced.
When numerical lower limits and numerical upper limits are listed here, from arbitrary lower limit to the scope of arbitrary upper limit Should be considered.

Claims (23)

1. the method forming the ring-shaped component that can be used as inner liner, wraps up sheet material including round assembly drum Forming the ring-shaped component of the seam of overlap to produce the opposite edges with overlap, described sheet material has The modulus more than about 6.5MPa that with good grounds ASTM D412-92 measures,
The edge of wherein said seam is modified before parcel.
2. the process of claim 1 wherein that described sheet material is blown film or casting films.
3. the process of claim 1 wherein that described edge by producing a series of saws along described edge Teeth cutouts is modified.
4. the process of claim 1 wherein that described edge is modified by suppressing described edge.
5. the method for claim 4, wherein said edge is heated before pressing.
6. the process of claim 1 wherein and modify described edge as follows: along the length of described sheet material Apply tension force until its fracture is by described sheet cutting.
7. the method for claim 6, produces a series of wearing the most before cutting along described edge Hole.
8. the process of claim 1 wherein that described edge by producing a series of fibres along described edge Silk is modified.
9. the process of claim 1 wherein that described ring-shaped component is dynamic vulcanization alloy.
10. including the goods that can be used as the ring-shaped component of inner liner, described ring-shaped component has basis The modulus more than about 6.5MPa that ASTM D412-92 measures,
Wherein said ring-shaped component has lap seams and described assembly at described lap seam Thickness is equivalent to the average thickness of described assembly.
11. methods forming the ring-shaped component that can be used as inner liner, including round assembly drum wrap sheet Material forms the ring-shaped component of the seam of overlap, described sheet material to produce the opposite edges with overlap There is the modulus more than about 6.5MPa measured according to ASTM D412-92,
Wherein said sheet material is reduced to greatly from more than or equal to about 2x in the gross thickness of lap seam About x, wherein x is the average total thickness of described sheet material, and the edge of wherein said seam is at parcel Front modified.
The method of 12. claim 11, wherein said edge is a series of by producing along described edge Zigzag incision is modified.
The method of 13. claim 11, wherein said edge is modified by suppressing described edge.
The method of 14. claim 13, wherein said edge is heated before pressing.
The method of 15. claim 11, the wherein described edge of following modification: along the length of described sheet material Degree applies tension force until its fracture is by described sheet cutting.
The method of 16. claim 15, produces a series of wearing the most before cutting along described edge Hole.
The method of 17. claim 11, wherein said edge is a series of by producing along described edge Fibril is modified.
The method of 18. claim 11, wherein said ring-shaped component is dynamic vulcanization alloy.
19. goods formed by the method for claim 11.
The method of 20. claim 11, also includes:
Described assembly is extruded together with adhesive exterior and rubber curable layer by blow moulding equipment, its Described in adhesive phase between described assembly and described rubber curable layer, to form tubular products； With
Compressing described tubular products to form sheet material, wherein said sheet material contains at least six layer, including Assembly described in outer rubber curable layer, adhesive phase, two-layer, extra adhesive phase and extra outside Rubber curable layer.
The method of 21. claim 20, wherein said adhesive exterior is by selected from following material structure Become: binding agent combines glue, resorcinol formaldehyde latex, phenol formaldehyde resin, resorcinol, isophthalic Two fluosite, formalin and hexamethoxy methyl cyanuramide.
The method of 22. claim 11, is additionally included in described assembly and binding agent in casting films equipment Extrude together.
The method of 23. claim 22, wherein said binding agent is constituted by selected from following material: viscous Mixture combines glue, resorcinol formaldehyde latex, phenol formaldehyde resin, resorcinol, resorcinol first Urea formaldehyde, formalin and hexamethoxy methyl cyanuramide.
CN201480074314.4A 2014-01-30 2014-11-14 Method of preparing an annular component useful as an air barrier and air barrier Pending CN105939842A (en)

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WO2015116302A1 (en) 2015-08-06

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Application publication date: 20160914